Method of preparing molecularly oriented copolymerizates of acrylonitrile and other monoethylenic monomers



Patented Mar. 11, 1947 OFFICE METHOD OF PREPARING MOLECULAR- LY ORIENTED COPOLYMERIZATES F ACRYLONITRILE AND OTHER MONO- ETHYLENIC MONOMERS Gaetano F. DAlelio, Northampton, Mass, as-

signor to Pro-phy-lac-tic Brush Company, Northampton, Mass., a corporation of Delaware No Drawing. Application February 25, 1944,

' Serial No. 523,905

3 Claims. (Cl. 260-32) The present invention relates to films, filaments and fibers fabricated from copolymerizates of acrylonitrile which articles are characterized by (1) having orientation of the polymer molecules parallel to the major axis and (2) having characteristic X-ray diffraction patterns. The particular object of this invention is to provide a method of preparing such fibers and filaments.

As is well known, polyacrylonitrile possesses characteristic properties in that it has a very high softening point and is extremely resistant to the solvent action of many bodies. Likewise, polyacrylonitrile is far too hard and brittle and too insoluble and possesses too high a, softening point to be used in extruded or precipitated bodies for the fabrication of articles characterized by having orientation of the polymer molecules parallel to the major surface of the article.

In copending applications of mine, Serial Nos. 445,808, filed June 4, 1942; 449,678, filed July 3, 1943; 523,901, filed February 25, 1944; 523,902, filed February 25, 1944; 523,903, filed February 25, 1944; 523,904, filed February 25, 1944, it was shown that the properties of the polyacrylonitrile could be altered considerably even when small amounts of other monomers are used in the preparation of certain copolymers. In the above mentioned applications, it was also recognized that these copolymers were capable of being converted as, for example, by cold drawing, into products and structures wherein the molecules have been oriented so that they are parallel with the major surface and whereby the formed structures exhibit characteristic X-ray diffraction patterns. However, I have now discovered another method of accomplishing much the same results, the method being more advantageous with certain materials and under certain conditions.

By the term a copolymerizate of acrylonitrile" is meant a copolymer of acrylonitrile with other polymerizable monoethylenic unsaturated monomers or materials wherein the acrylonitrile is substantially the major component of the copolymer. In general such copolymers possess at least 50 but not more than 85% acrylonitrile. The other copolymerizable ingredient or ingredients may be ethylenic unsaturated compounds, for example, the acrylates, methacrylates, itaconates, maleates, fumarates, vinyl ethers, vinyl aryls, etc., or mixtures of these. These monomers may be used alone or in conjunction with other monomers. These copolymers of acrylonitrile, when subjected to treatment of the type'more fully described hereinafter, to form them into filaments, films, fibers, rods, tubes, and the like, exhibit,

when cold drawn, a characteristic crystalline X- ray diffraction pattern in which the molecules are oriented parallel to the major axis. Articles so characterized have a very high degree of flexibility and ultimate tensile strength exceeding that of articles, such as films and filaments formed from the use of polymeric bodies in the usual manner.

It is common practice in the manufacture of sheets, filaments, and fibers to dissolve the polymer in a suitable solvent and cast or extrude a concentrated solution of the polymer to the desired form. This process requires a high degree of solubility in the polymer. This method is not readily applicable to all or many of the heteropolymers of 'acrylonitrile because many of the heteropolymers are only slightly soluble even in some of the more highly active polar solvents While others are completely insoluble even in these same active solvents. Of the copolymers which exhibit solubility it has been possible to prepare solutions up to approximately 10%. Such dilute solutions are not satisfactory from an industrial standpoint since they involve the use of large amounts of solvents and involve expensive recovery systems and include toxicity, fire and explosion hazards, if such solvents are inflammable or toxic.

Such dilute solutions ofacrylonitrile copolymers are not altogether satisfactory in the preparation of the formed articles of this invention because large quantities of such highly active solvents as the nitrohydrocarbons must be used, and the removal of the major proportion of the solvent entails subjecting the copolymer to extended heat treatment wherein some loss of tensile strength, loss of form and high porosity in the finished filament or sheet may occur.

I have now discovered that it is possible to eliminate most of the difficulties of the solution method by utilizing gels of these copolymers. As is well known, a solution difiers from a gel generally speaking, in that in solutions, the molecules of the solute (polymer) are dissolved substances dispersed among those of the solvent (nitrohydrocarbon) and are spatially movable whereas a gel is the apparently solid jelly-like material in which the molecules of the solute are spatially fixed and therefore is much more resistant to dimensional change when transferred from one container to another. A gel usually involves a reversal of the phase, that is, the solvent becomes the solute and the solute becomes the solvent. The difference between a solution and a gel is illustrated in the following:

A solution of 90 parts of nitromethane and parts of the copolymer of acrylonitrile (70%) and vinyl ether (30%) is readily prepared by agitating the polymer in the nitrohydrccarbon. Within a period of a few hours, a liquid but viscous solution of the polymer in the solvent is obtained. If the nitromethane is removed from the solution as by evaporation, under heat or heat and vacuum, the viscosity is considerably increased and a solution which is much more viscous at room temperature is obtained. When the concentration of the polymer reaches about 18%, a mass is obtained which is a gel at room temperature but which may be easily reliquefied by heating above room temperature. Under vacuum and heat it is possible to concentrate solutions to obtain gels containing 25 to 80% or more of the polymer in the nitrocarbon; However, it is not necessary to first prepare a solution of the copolymer to obtain the gels used in the practice of this invention. The preferred method involved preparing the gel directly. These gels may be prepared by adding the desired amount of gelation solvent, for example, a nitrohydrocarbon; directly to the copolymer and forming the gel, by processing in suitable mixing equipment such as in a heated dough mixer, Banbury mixer, rubber or plastic milling rolls, etc.

In this way, it is possible to prepare gels of much higher concentration than by the solution method. Thus, it is possible to prepare a gel of 50 parts of gelation solvent and 50 parts of the copolymer of 70 parts of acrylonitrile and 30 parts of another monoethylenic unsaturated monomer, for example, vinyl butyl ether. At room temperature, such a gel is a tough cohesive rubbery jelly or dough-like mass, while at higher temperatures, it is an extremely viscous, flowableliquid which may be readily worked through orifices at relatively low pressures, of the order of 20 to 100 pounds per square inch.

In the practice of this invention, however, I prefer to use gels wherein the concentration of polymer is of the order of to of polymer. When heated to temperatures substantially above room temperature, that is, between 65 and 95 0., these gels may be readily filtered through candle filters to remove insoluble particles, ungelled particles, solid contaminants, etc.

Many advantages of this processresult. Through its practice, it is possible to realize con-.- siderable economy in solvents, time, and equipment investment. Furthermore, the problems connected with th recovery of the gelation solvent are materially reduced. The method is particularly advantageous in the manufacture of fibers, monofils, and sheets. Considerable dim culty has been encountered in attempting to prepare fibers from solutions of acrylonitrile copolymers. Such solutions are extremely viscous and contain such a small amount of the polymer that a satisfactory filament is not formed when the material leaves the orifice of the extruding equipment. Furthermore, the small amount of polymer combined with the rapid evaporation of the solvent causes the article to be distorted, as it leaves the orifice. These difliculties are substantially eliminated when the gel is used instead of the solution. Once prepared and filtered, the gel is degel.

is transferred from these heated reservoirs to the spinnerets by constant pressure pumps. The

spinnerets are likewise maintained at a temthe spinning easily started so that the threads may be led through the drying chamber to winding rolls, etc., to be collected on bobbins. The filaments formed from this liquefied gel are uniform in size and free of distortion in contrast to those formed from solutions wherein little uniformity and much distortion occur. This is probably so because as the plastic mass leaves the spinneret, the filament is immediately converted to a rigid gel by the drop in temperature as it passes out of the spinneret. Possibly the change to a rigid gel is accelerated by loss of solvent as the material emerges from the orifice and the pressure to which it was subjected in passing through the orifice is released. The formed material is then subjected to drying at a temperature sufficient to remove a part of the gelation solvent so that the gel does not reliquefy even when heated to progressively higher temperatures.

0n the other hand, when solutions are spun, temperatures higher than the spinneret temperatures mustbe used to remove the solvent. In the solution process, when the filament containing such a high quantity of solvent is subjected to higher temperatures, an immediate drop in viscosity occurs so that fibers lacking uniform dimensions are obtained, and considerable difiiculty is encountered in initiating the spinning process and in keeping the spinning process operating continuously. Furthermore, in spinning from solutions, higher drying temperatures are required,,with the result that the fibers tend to be porous and more brittle when compared with those prepared from the gelation process.

In the practice of my invention, the regelled polymer is dried in a suitable chamber to remove a greater part or substantially all of the solvent and .then is subjected to a cold drawing operation. This cold drawing is accomplished by stretching the monofil. This is done preferably at room temperature or substantially above room temperature, but below the temperature of the melting point or decomposition point of the polymer. This cold drawing is accomplished in many of numerous ways, such as, by passing the monofil consecutively over diiferential rolls travelling at different speeds and the degree of cold drawing may be achieved by stretching of the order of to 600% of the original length of the monofil. The temperature of the drawing may be room temperature or if the temperature desired is carbons, glycols, glycerine, diglycerine, are satisfactory liquid media to be used in eiiecting the cold drawing of these materials. Gaseous media likewise may be used. Air is satisfactory at lower temperatures. When higher temperatures are desired, inert gases, such as carbon dioxide, nitrogen, hydrogen, etc., are satisfactory.

The filament and sheet materials, as prepared by extrusion and drying is not molecularly oriented. It is only after the cold drawing process that it exhibits the characteristic X-ray diffraction pattern indicative of crystalline orientation. On the other hand, the increase in tensile strength and flexibility after the cold drawing is remarkable. As a rule, acrylonitrile copolymerizates have a tensile strength ranging in order from 5,000 to 10,000 pounds per square inch. When cold drawn to the extent of 200 to 500%, tensile strengths of the order of 15,000 to 40,000

tioned heretofore. By this method many plasticizers which normally do not possess good compatibility with the polymer may be incorporated into the polymer. Suitable high-boiling plastior 50,000 pounds per square inch are readily ob- 5 cizers may be mentioned, the polybasic esters of tainable. cyano-alcohol and of the nitro-alcohols, such as, In the practice of this invention, the nitrohythe esters of phthalic, succinic, sebacic, tetrahydrocarbons were found to be the most suitable drophthalic, endomethylene tetrahydrophthalic, liquids for use in forming the gel. since these acetyl citric acids, etc. It is not necessary that solvents are used in intermediate stages in the 10 all of the carboxyl groups of the polybasic acid practice of this invention, it is desirable that they be esterified with the cyano alcohol or the nitrohave low boiling points so that they may be realcohol. Thus, in a dicarboxylic acid, one carmoved readily from the copolymer mass. Among boxyl group may be esterified with the cyano suitable nitro-hydrocarbon solvents may be menalcohol and the other with the methyl, ethyl, tioned nitro-aliphatics, such as nitro-methane, p opyl, butyl alcohols, etc.; nd in a tricarboxylic nitroethane, nitropropane, nitrobutane, the niacid, it is suflicient if one or two of the carboxyl tro-aromatics and cyclo-aliphatics, etc, Al groups are esterified with another alcohol. Also, there may be used in connection with them, but as s itab e plasticizers r the Products of this preferably in minor proportions, certain ketones, invention may be mentioned the condensation for instance, acetone, methyl ethyl ketone, methp o u ts f acrylonitrile with organic p u ds yl propyl ketone, methyl'amyl ketone, acetophecontammg the ti hydrogen u or exnone, phorone, methyl chlorphenyl ketone, methp v t s t o product of an acrylonia yl nitrophenyl ketone, chlorethyl nitrophenyl ketrile and acetone wherein the hydrogens of the tone, diacetone alcohol, acetonyl acetone, acetyl CHa groups of the'acetone may be substituted acetone, biacetyl, methyl acetoacetic ester, ethyl y flflm one t x p-cya y o p gs. acetoacetic ester, etc.; the nitro-alcohols such Other plasticizers which may be prepa ed y the as, 2-nitro-1-ethanol, 2-nitro-1-propanol, 2-nlcondensation of acrylonitrile with organic comtro-l-butanol, 2-nitro-1-pentanol, etc.; esters of pounds containing act hydrogen e the 0011- the aforementioned nitro-alcohols, such as, the densation produc wi alcohols. r l formate, the acetate, the propionate, the butyrate, with phenyl ethyl lcohol, phcnoxyethyl al etc; the ethers of the aforementioned nitro-alcomethoxy h le lyc l, ethoxydiethylene glyhols, for example, the methyl, the ethyl, the procol, phenoxydi t e g y densation pyl, and the butyl ethers, etc; the cyano-alcoproducts of acrylonitrile with such compounds as hols, for example, lactonitrile, the addition prodthe acetoacetic esters, malonie esters, acetyl aceucts of the lower-boiling aldehydes, and ketones 190118, d certain p y i ydrocarbons conwith hydrogen cyanide, for example, the reaction tainin t e products of hydrogen cyanide with acetaldehyde, propionaldehyde, acetone, methyl ethyl ketone, etc.; the esters of the cyano-alcohols, for example, the formate, the acetate, the propionate, etc.; 40 ma the condensalflon P s of y othe ethers of the cyano-alcohols, for example, the mtme Wlth cyano and mtm alcohols, e methyl, ethyl, propyl e150,, th certain phos The fibers and smaller articles produced acphates such as trimethyl and triethyl phosphates cordmg to 31115 mvention may be Woven into may likewise be used highly insoluble and chemically resistant cloth For certain compositions, if it is desirable, such for use in filter cloths and handling e cals gelation solvents as pyridine, quinoline, acetic anand the like- They may also be s d for texhydride, acetic acid, etc., may be used, but they tiles, for example, cloth, hosiery, articles of clothare undesirable from a health and safety factor ins, etc. In the form of sheets, they may be or from the corrosion factor encountered in the used as p c e coatings. awnings, ain o t manufacturing process. The foregoing gelation so shower curtains, aprons, hospital b d h n agents are mentioned by way of illustration and containers for hydr o O s, asoline, keronot as limitations, except as limitations are found sene, vasoline, ointments, etc. in the claims appended hereto, since I believe my- The following example illustrates how this inself to be the first to discover the possibility of Vention y be carried into effect: making a gel from the materials in question and P t the process of utilizing the gel. Likewise, it may Distilled Water ar 5 400 be desirable to introduce a certain amount of Polyvinyl alcohol n 2 plasticizmg material in these copolymers and it Benzoyl peroxide 1 is desirable that such plasticizer compounds be Monomer mixtur T introduced into the polymer mass after the gela- 6O 100 tion of the mass has been accomplished by the AS examples f yp c l monomer mixtures which gelatioh s sm y be used in the above formulation I may use.

Parts Parts Parts Parts Parts Parts Parts Parts iiil?iilltii:::i:i Z2 .1? 22 32 "-19. 33 32 A viny ether 27 10 25 Amaleic ester 5 10 5 Styrene 1o 15 Since it is diflicult to incorporate plasticizers The polyvinyl alcohol is dissolved in the water into the copolymers of this invention by the ordiprior to the addition of the remaining ingredinary milling process, I prefer to accomplish this ents. The mixture is then heated under agitaby adding the plasticizer either to a solution or tion at 50 to C., until the polymerization is to a gel of the copolymer in the solvents mencompleted. The granular material is in the form of spheres which are filtered ofl, washed with distilled water and dried in a vacuum oven at 50 C. The copolymers of the above compositions are mixed with sufilcient gelation solvent, e. g., nitromethane or ethane in the ratio of to parts of polymer to 70 to 80 parts of gelation solvent. The mixture of polymer and gelation solvent is processed in a dough mixer at 85 to 95 C., until a homogeneous mass which is a liquefied gel is obtained. At these temperatures the mass is a liquid but when allowed to cool to room temperature, it solidifies to a rubbery jelly-like mass, i. e., to a gel. The liquefied gel is passed through candle filters to remove all insoluble, ungelled, and foreign particles. The filtered liquefied gel is then transferred to reservoirs in which it is degassed under vacuum while still in a liquid state. From these reservoirs the liquefied gel is pumped through orifices to give the material the desired shape, that is, through spinnerets for the preparation of fibers or monofils, or, through a die in the form of a slit for the preparation of sheets. As the formed plastic mass leaves the orifice, it resets to a gel by passing through an area whose temperature is lower than the temperature at which the orifice is maintained. The extruded material is then subjected to a drying process. The drying is accomplished at a tem- 'perature sufilcient to remove a quantity of the gelation solvent so that the gel does not reliquefy even when heated to progressively higher temperatures. For example, in spinning a fiber, the

spinneret temperature may bemaintained about at 80 C. On leaving the spinneret, the temperature of the monofil may be dropped to room temperature or even up to C. for a distance of a few inches before entering a drying chamber. During thiseshort r interval the material changes to,a gel. The immediate area of the drying chamber into which the filament passes may be maintained at approximately 50 C. on reaching this area, sufiicient surface evaporation and drying of the monofiloccurs to form a rigid shell around the remaining. gel mass, thereby giving it added strength. The drying of" the filament may be continued at this same temperature in a relatively long drying chamber. If a shorter chamber is used the filament can be passed directly into a region of higher temperature without liquefying the gel because of the partially dried shell existing around the interior gel. The completely dried or partially dried monofil is led from the drying chamber to the cold drawing mechanism which consists of at least two differential rolls whose speeds are adjusted so that any degree of cold drawing up to the elastic limit of the drawn monofil vcan be attained. Usually the extent of cold drawing lies within the limits of 100 to 600%.

In the practice of the cold drawing of this invention, I prefer to work in a range of 200 to 500%. Preferably, cold drawing temperatures between 25 and C. are preferred. After the cold drawing, the filaments may be subjected to a twisting operation and collected on bobbins. The filament, as prepared by extrusion of the gel, and drying is not molecularly oriented.

I claim:

1. A cohesive workable reversible gel adapted to the preparation of shaped or molecularly oriented structures which consists of a liquid nitrohydrocarbon and the co-polymerization product of a mixture comprising at least 55 percent but not more than of acrylonitrile and another polymerizable monomer containing a single olefinic double bond, the copolymerization product forming from 20 to 50 percent of the gel.

2. A cohesive workable reversible gel adapted to the preparation of shaped or molecularly oriented structures which consists of nitromethane and the co-polymerization product of a mixture comprising at least 55 percent but not more than 85% of acrylonitrile and another polymerizable monomer containing a single olefinic double bond, the copolymerization product forming from 20 to 50 percent of the gel.

3. A'cohesive workable reversible gel adapted to the preparation of shaped or molecularly oriented structures which consists of nitroethane and the copolymerization product of the mixture comprising at least 55 percent but not more than 85 percent of acrylonitrile and another copolymerizable monomer containing a single olefinic double bond, the copolymerization product forming from 20 to 50 percent of the gel.

GAETANO F. D'ALELIO.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Bogin et al,, (1) article in Ind. Eng. Chem., pages 1091-1096, SeptTY1942. Bogin (2) "How the Coating Industry is Using the Nitroparaflins" (20 pp.) reprinted from Paint, Oil, and Chemical Review, issues of Aug. 27, Sept. 10 and 24, and Oct. 1942. (Copy in Div, 56.)

Lewis et al.; Industrial Chemistry of Colloidal and Amorphous Materials, page 225, published by Macmillan Co., N. Y. 1943. (Copy in Div. 50.) 

